TW201215615A - Isosorbide derivatives and liquid crystal displays comprising the same - Google Patents

Abstract

An isosorbide derivative of Formula (I) is provided. In Formula (I), Z is -CH2-CH2-, -CH=CH-, -C ≡ C-, -CH2-O-, -CH2-S-, -CH=N-O-, -CO-O-, -CO-S-, single bond, -ph-, -CO-O-ph- or -CO-O-ph-CO-O-, wherein ph represents benzene, R1 and R2 are, independently, C1-25 alkyl, -CN, -NCS, -CX3 or -OCX3, wherein X represents halogen, and m and n are, independently, 0, l or 2. The invention also provides a liquid crystal display including the isosorbide derivative.

Description

201215615 VI. Description of the Invention: [Technology of the jaw region of the invention] The present invention relates to an isosorbide derivative, and more particularly to an isosorbide derivative which is miscellaneous to a liquid crystal display. [Prior Art] In recent years, due to the development of the liquid crystal industry, liquid crystal materials with various needs have been developed one after another. Among them, cholesteric liquid crystal has bistability and no applied voltage. The picture performance can still be maintained, so there is an opportunity to become a new generation of flat display technology. The cholesteric liquid crystal material has both a spiral structure and a liquid crystal property. The helical structure is usually formed by doping a chiral dopant into a cholesteric liquid crystal molecule without palmarity. Therefore, the helical twisting power (HTP) of the palmitic molecule is the main factor determining the degree of sinusoidal liquid crystal torsion. In general, each pair has a different HTP for its palm structure. A chiral dopant is an optically active substance. When a palmitic dopant is added to a liquid crystal having a nernatic phase, the liquid crystal is converted into a cholesteric liquid crystal phase. The size of the helical torsion (HTP) of the palmitic molecule is mainly determined by the characteristics of the palmitic dopant itself, but is also affected by, for example, the nematic liquid crystal host and temperature. 201215615 SUMMARY OF THE INVENTION One embodiment of the present invention provides an isosorbide derivative having the following chemical formula (I):

Wherein Z is -CH2-CH2-, -CH=CH-, -OC-, _CH2-0-, -CH2-S-, -CH=N-0-, -C0-0-, -CO-S-, Single bond, -ph-, -C0-0_ph_* -C0-0, ph-C0-0-, wherein ph is phenyl; R] and R2 are independently a carbon number of 1 to 25 £ alkyl, -CN, - NCS, -CX3 or -0CX3, wherein X is a halogen; and m and η are independently 0, 1, or 2. An embodiment of the present invention provides a liquid crystal display including: an upper substrate; a lower substrate disposed opposite the upper substrate; and a liquid crystal layer disposed between the upper substrate and the lower substrate, including an isosorbide An isosorbide derivative having the following chemical formula (I): 201215615

Wherein Z is -CH2_CH2_ ' _CH=CH-, -CSC.·, -CH2_0-, -CH2-S -, -CH=N-0-, -CO-O·, -CO-S-, grass bond, - Ph-, -CO-O-ph- or -CO-O-ph-CO-O-, wherein ph is phenyl, K and R2 are independently alkyl having 1 to 25 carbon atoms, -CN, -NCS, -CX3 or -〇CX3, where x is a halogen, and m and η are independently 0, 1, or 2. The present invention develops a novel isosorbide derivative for a chiral dopant whose core structure is composed of an isosorbide and is treated with piperazjne as its Side key structure. The isosorbide derivative of the present invention has been proved to be effective by the test: the temperature of the cholesteric liquid crystal (ch〇iesteric HqUid cryStal) is stable (for example, its temperature dependence gamma dependence) Less than or equal to Q, 2 nm / <> c), in addition, the isosorbide derivative also has a dry twisting power (HTP) (for example, can be large = 45 μηι) 'for raising cholesterol The degree of spiral twist of the liquid crystal is quite helpful. In order to make the above objects, features and advantages of the present invention more comprehensible, the following is a description of the preferred embodiment of the present invention, and the following is a detailed description of the following: 201215615 [Embodiment] In one embodiment of the invention, there is provided an isosorbide derivative having the following chemical formula (I):

In the formula (I), Z may be -CH2_CH2·, -CH=CH-, -C^c-, -CH2-0-, -CH2-S-, -CH=N-0-, -C0-0 -, -C0_S-, single bond, -ph-, -C0-0-ph- or -C0-0-ph-C0-0- 'The above ph represents the base.

Ri and R2 may independently be an alkyl group having 1 to 25 carbon atoms, -CN, -NCS, -CX3 or -0CX3, and X represents a halogen. m and η can be independently 0, 1, or 2. Specific examples of the isosorbide derivatives of the present invention are listed below:

(Compound A_2C1), 201215615

CjHn-N

N-C5Hn (Compound A-2C5),

(Compound A-2IC5),

(Compound A-2BC5),

C5h„

(Compound A-C1C5),

(Compound A-2aBCl), 5 8 201215615

(Compound A-2CF3). An embodiment of the present invention provides a liquid crystal display including an upper substrate, a lower substrate disposed opposite the upper substrate, and a liquid crystal layer disposed between the upper substrate and the lower substrate, including an isosorbide a derivative having the following chemical formula (1):

In the chemical formula (1), Z may be -CH2-CH2-, -CH=CH-, -C^C-, -CH2-0-, -CH2-S-, -CH=N_0-, -C0-0-, -C0_S-, single bond, -ph-, -C0-0-ph- or -C0-0~ph-C0-0-, the above ph represents phenyl. R] and the ruler 2 may independently be an alkyl group having 1 to 25 carbon atoms, -CN, -NCS, 201215615 -cx3 or -ocx3, and the above χ represents _ 素. m and η may independently be 〇, ι or 2. The isosorbide derivative of the present invention can be doped to a liquid crystal display such as a cholesteric liquid crystal. The present invention develops a novel isosorbide (is〇s〇rbide) derivative to a chiral dopant whose core structure is composed of an isosorbide and is (piperazine) as its side chain structure. The isosorbide derivative of the present invention has been tested and proved to be effective in maintaining temperature stability of, for example, cholesteric liquid crystal (for example, temperature dependence can be made less than or Equal to 〇.2nmrC), in addition, the isosorbide derivative also has a large heiicai twisting p〇wer (HTP) (for example, can be greater than 45μιη i) 'is quite equivalent to the degree of helical twist of the cholesteric liquid crystal s help. [Examples] [Example 1] φ Synthesis of isosorbide derivative of the present invention 1 Compound A-2C1

To

First, '2.2 g of 4-[4-methyl-piperazin-l-yl]-benzoic acid (10 mmol) and 2.43 10 201215615 g of 1 , 1"· 基基二_β坐(l,l"-Carbonyldiimidazole, CDI) (15mmol) was placed in a 100 ml double neck round bottom bottle. Thereafter, under a nitrogen (n2) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of a solution. Next, 0.45 g of Isosorbide (3 mmol) was placed in another round bottom flask, and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Subsequently, recrystallization was carried out using decyl alcohol (MeOH) to obtain 1.15 g of Compound A-2C1 (yield: 70%) as a white solid. [Example 2] Synthesis of isosorbide derivative of the present invention 2 Compound A-2C5

First, 2.76 g of 4-[4-Pentyl-piperazin-l-yl]-benzoic acid (10 mmol) and 2.43 g of 4-[4-Pentyl-piperazin-l-yl]-benzoic acid (10 mmol) 1,1"-Amino- 11-mole (l,l"-Carbonyldiimidazole, CDI) (15 mmol) was placed in a 100 ml double neck round bottom bottle. Thereafter, under a nitrogen (N2) atmosphere, 30 ml of anhydrous tetrahydrofuran (Tetrahydrofuran, π 201215615 THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of a solution. Next, 0.45 g of isosorbide (3 mmol) was placed in another round bottom flask and dissolved in tetrahydropyrene (THF) under ice. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. A yellow solid was obtained after drying. Subsequently, recrystallization was carried out using decyl alcohol (Me〇H) to obtain 1.25 g of Compound A-2C5 in a yield of 63%, which was white solid. [Example 3] Synthesis of isosorbide derivative of the present invention 3 Compound A-2IC5

First, 2.76 g of 4-[4-(1-methyl-butyl)-fluorene-beta-methyl-1-yl]••benzoic acid (4-[4-(l,Methyl-butyl)-piperazin- L-yl]-benzoic acid) (1Ommol) and 2.43 g of hydrazine, Γ'-carbonyldiimidazole (CDI) (15 mmol) were placed in a 1 liter double neck round bottom flask. Thereafter, under a nitrogen (N2) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged, and after heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the solution A. 12 201215615 Next, 0.45 The gram of isosorbide (3mmol) was placed in a separate round bottom bottle and dissolved in tetrahydrofuran (THF) in an ice bath. After the addition of sodium hydride (NaH), the preparation of the B solution was completed. After a small percentage, the above A solution is poured into the b solution and stirred to room temperature for about one hour. After the pomelo is dried, 'a yellow solid can be obtained. Then, using methanol (MeOH) to stare and recrystallize, 129 g of compound A_2IC5 was obtained in a yield of 65%, and the appearance was white gj. ❿ [Example 4] Synthesis of isosorbide derivative of the present invention 4 Compound A-2BC5

First, 3.52 g of 4-[4-(4-pentyl-phenyl)-piperazin-1-yl]•benzene•carboxylic acid (4_[4-(4-Pentyl-phenyl)-piperazin_i_yi]_benz〇ic Acid) (lOmmol) and 2.43 g of 1,1,-carbonyldiimidazole (CDI) (15 mmol) were placed in a 100 ml double neck round bottom bottle. Thereafter, under a nitrogen (N2) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. The preparation of the A solution was completed by heating to reflux for four hours and then "putting to room temperature". Next, 0.45 g of Isosorbide (3 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, the preparation of the B solution was completed by adding sodium hydride (NaH). After the 13th 201215615 "7] temple, the above A solution was poured into the B solution, and stirred to room temperature about - J, after drying, a yellow solid was obtained. Subsequently, using decyl alcohol (MeOH) to carry out re-, ̄, cation, 1.61 g of Compound A-2BC5 was obtained in a yield of 66% of the appearance as a white solid. [Example 5] Synthesis of isosorbide derivative of the present invention 5 Compound A-C1C5

First, '2.2 g of 4_[4·methyl-piperazinyl]-benzoic acid (4 [4 Methyl-piperazin-l-yi]_benzoic acid) (10 mmol) and 2.43 g of 1,1 - _ Base sigmoid (i, i,, _Carbonyldiimidazole, CDI) (15 mmol) was placed in a 1 liter double neck round bottom bottle. Thereafter, 30 ml of anhydrous tetra-argon was introduced under nitrogen (n2). Tetrahydrofuran (φ THF). After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of a solution. Next, 1.9 g of Isosorbide (13 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution' and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Next, column chromatography (with EA:HEX = 1:1 as a water-filled liquid) was carried out to obtain 2.1 g of an intermediate 14 201215615 (6 mmol) in a yield of 66%. Thereafter, 2.21 g of 4-[4-Pentyl-piperazin-l-yl]-benzoic acid (8 mmol) and 2_43 g of 1 , 1"·基基二咪0坐(Ι,Γ'-Carbonyldiimidazole, CDI) (15mmol) was placed in a 1 liter double neck round bottom bottle. After that, it was 'into 30' under nitrogen (n2) environment. ML of anhydrous tetrahydrofuran (THF) ° after heating for four hours, put it to room temperature, complete the preparation of c solution. • Then 'put the above intermediate in another round bottom bottle, and ice Under the bath, tetrahydrofuran (THF) was added to dissolve. After that, sodium hydride (NaH) was added to complete the preparation of the D solution. After two hours, the above C solution was poured into the D solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Then, using decyl alcohol (MeOH) to recrystallize, 1.83 g of the compound A-C1C5 was obtained in a yield of 50%, and the appearance was white solid. Example 6 Synthesis of an isosorbide derivative of the present invention 6 Compound A-2aBCl

First, '3.40 g of 4-(4-carboxy-phenyl)-piperazinecarboxylic acid 4-(4-carboxyboxyl-phenyl)-piperazin-l-carboxylic acid_p-tolyi ester ( 1 〇 inmol) and 2.43 g of 1,1''-carbonyldiimidazole 201215615 (Ι, ''-Carbonyldiimidazole, CDI) (15 mmol) were placed in a 100 ml double neck round bottom bottle. Thereafter, under a nitrogen (N2) atmosphere, 30 ml of anhydrous tetrahydrofuran (Tetrahydrofuran, THF) was charged. After heating under reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the A solution. Next, 0.45 g of Isosorbide (3 mmol) was placed in another round bottom flask, and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Subsequently, recrystallization was carried out using decyl alcohol (MeOH) to obtain 1.54 g of Compound A-2aBCl in a yield of 65%. [Embodiment 7]

Synthesis of isosorbide derivatives of the invention 7 Compound A-2CN

First, 2.31 g of 4-(4-cyano-piperazin-l-yl)-benzoic acid (10 mmol) and 2.43 g of 1, Γ'-Carbyldiimidazole (CDI) (15 mmol) was placed in a 100 ml double neck round bottom bottle. Thereafter, under a nitrogen (N2) atmosphere, 30 ml of anhydrous Tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of 16 201215615 of solution A. The receiver's o. 45 g of isosorbide (3 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. After the addition of sodium hydride (NaH), the preparation of the B solution was completed. After two hours, the above A solution was poured into the b solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Subsequently, recrystallization was carried out using methanol (Me〇H) to obtain 0.9 g of Compound A-2CN in a yield of 68%. [Example 8] Synthesis of isosorbide derivative of the present invention 8 Compound A-2CF3

• First, 2.74 grams of 4-(4-trifluoromethyl-piperazin-l-yl)-benzoic acid (10 mmol) and 2.43 Cg of CDI) (15 mmol) was placed in a 100 ml double neck round bottom bottle. Thereafter, 30 ml of anhydrous Tehydrohydrofuran (THF) was placed in a nitrogen (N2) atmosphere. After heating under reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the A solution. Next, 0.45 g of isosorbide (3 mmol) was placed in 17 201215615 in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. A yellow solid can be obtained after the dried grapefruit. Subsequently, recrystallization was carried out using methanol (Me〇H) to obtain 1.18 g of Compound A.. 2CF3 in a yield of 60%. [Example 9] Helix torsion (HTP) and temperature dependence of isosorbide derivatives of the present invention Isosorbide derivatives (Compounds A-2C1, A-2C5, A-2IC5, A-2BC5, A-C1C5, A-2aBCl, A-2CN, A-2CF3) related physicochemical properties, such as helical twisting power (HTP) and temperature dependence (Ιλ/dT) It is shown in Table 1. The measurement temperature is 20~50 °C.

❿ A- A- A- A- A- A- A- A- 2C1 2C5 2IC5 2BC5 C1C5 2aBCl 2CN 2CF3 HTP 45 47 46 46 45 48 45 47 (μπΓ1) άλ/dT +0.03 -0.19 -0.16 -0.1 1 - 0.2 -0.14 -0.12 -0.17 (nm/°C) 18 201215615 As seen in Table 1, the isosorbide derivatives of the present invention (compounds A-2C1, A-2C5, A-2IC5, A-2BC5) , A-C1C5, A-2aBCl, A-2CN, A-2CF3) have large helical twisting force (HTP), for example, both are greater than 4541^1, and their temperature dependence is low, for example, less than or equal to OJnm/aC Therefore, it is quite suitable for application to liquid crystals such as cholesteric liquid crystals. While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and retouched without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application. 201215615 [Simple description of the schema] Benefits. ό, [Main component symbol description]

Claims (1)

201215615 VII. Scope of application: 1. An isosorbide derivative having the following chemical formula (I): Wherein Z is -CH2-CH2-, -CH=CH-, -C tri C-, -CH2-〇-, -CH2-S-, -ph-, -CO-O-ph- or -CH=N- 0-, -CO-O-, -CO-S-, single bond -CO-O-ph-CO-O-, wherein ph is phenyl; R] and R2 are independently an alkyl group having 1 to 25 carbon atoms, -CN, -NCS, -cx, or _ocx3, wherein X is an element; and m#n is independently 〇, 1 or 2. Straight 2. The isosorbide derivative as described in the patent application, the t sorbitol derivative includes: 201215615 3. A liquid crystal display comprising: an upper substrate; a lower substrate disposed opposite the upper substrate; and a liquid crystal layer disposed between the upper substrate and the lower substrate, comprising an isosorbide derivative , having the following chemical formula (I): 22 201215615 (i) where Z is -CH2-CH2_,, CH=CH-, -OC-, -CH2-0-, -CH2-S-, -CH=N-0-, -C0-0-, -CO- S-, single bond, -ph-, -C0-0-ph- or -CO-O-ph-CO-O-, wherein ph is phenyl, R] and R2 are independently carbon _ number 1~25 Alkyl, -CN, -NCS, -CX3 or -OCX3, wherein X is a halogen, and m and η are independently 0, 1, or 2. 4. The liquid crystal display of claim 3, wherein the liquid crystal display is a cholesteric liquid crystal display. twenty three